EP1648958B1 - Powdery composition of a polymer and a flameproofing agent containing ammonium polyphosphate, method for the production thereof, and moulded body produced from said powder - Google Patents
Powdery composition of a polymer and a flameproofing agent containing ammonium polyphosphate, method for the production thereof, and moulded body produced from said powder Download PDFInfo
- Publication number
- EP1648958B1 EP1648958B1 EP04766029A EP04766029A EP1648958B1 EP 1648958 B1 EP1648958 B1 EP 1648958B1 EP 04766029 A EP04766029 A EP 04766029A EP 04766029 A EP04766029 A EP 04766029A EP 1648958 B1 EP1648958 B1 EP 1648958B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- flame retardant
- polymer
- ammonium polyphosphate
- powder according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 title claims abstract description 153
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 229920001276 ammonium polyphosphate Polymers 0.000 title claims abstract description 52
- 239000004114 Ammonium polyphosphate Substances 0.000 title claims abstract description 46
- 235000019826 ammonium polyphosphate Nutrition 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000003795 chemical substances by application Substances 0.000 title description 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 70
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 58
- 238000000465 moulding Methods 0.000 claims description 34
- 239000004952 Polyamide Substances 0.000 claims description 29
- 229920002647 polyamide Polymers 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 29
- 229920000299 Nylon 12 Polymers 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000344 soap Substances 0.000 claims description 18
- -1 polypropylene Polymers 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 11
- 238000000110 selective laser sintering Methods 0.000 claims description 7
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000000539 dimer Chemical class 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 229920000571 Nylon 11 Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920000554 ionomer Polymers 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000010146 3D printing Methods 0.000 claims description 3
- 229920001634 Copolyester Polymers 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229930182556 Polyacetal Natural products 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000001226 reprecipitation Methods 0.000 claims description 2
- 229910001111 Fine metal Inorganic materials 0.000 claims 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims 2
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 claims 1
- 239000011369 resultant mixture Substances 0.000 claims 1
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000010276 construction Methods 0.000 description 7
- 238000000149 argon plasma sintering Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000005521 carbonamide group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006099 Vestamid® Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
Definitions
- the invention relates to a polymer powder which comprises at least one polymer and at least one flame retardant containing ammonium polyphosphate, a process for the preparation of this powder and moldings produced by layered application and fusion of this powder.
- One method which is particularly well suited for the purpose of rapid prototyping is selective laser sintering.
- plastic powders in a chamber are selectively exposed to a short laser beam, thereby melting the powder particles that are hit by the laser beam.
- the molten particles run into each other and solidify quickly back to a solid mass.
- PA 12 polyamide 12 powder
- the parts meet the high demands that are placed on the mechanical stress and thus come in their properties particularly close to the later series parts, created by extrusion or injection molding become.
- a PA 12 powder with a mean particle size (d 50 ) of 50 to 150 microns is for example according to DE 197 08 946 or DE 44 21 454 receives.
- a polyamide 12 powder having a melting temperature of 185 to 189 ° C, a melting enthalpy of 112 ⁇ 17 J / g and a solidification temperature of 138 to 143 ° C, as in EP 0 911 142 is used.
- pulverulent substrates in particular polymers or copolymers, preferably selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, polypropylene (N-methylmethacrylimide) (PMMI), polymethylmethacrylate (PMMA), ionomer, polyamide, copolyesters, copolyamides, terpolymers, acrylonitrile-butadiene-styrene copolymers (ABS) or mixtures thereof.
- polymers or copolymers preferably selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, polypropylene (N-methylmethacrylimide) (PMMI), polymethylmethacrylate (PMMA), ionomer, polyamide, copolyesters, copolyamides, terpolymers, acrylonitrile-butadiene-styrene copo
- a disadvantage of the polymer powders currently used are in particular their ease of ignition and flammability. This currently prevents the use of the above-described methods for use in small batches, for example in aircraft construction.
- the object of the present invention was therefore to provide a polymer powder, which allows for less flammability of the parts made therefrom with any of the methods described above.
- pulverulent compositions can be prepared by adding ammoniumpolyphosphate flame retardants to polymers or copolymers, from which moldings are melted by a layer-by-layer process in which areas are selectively melted or bonded together , can produce, which are significantly less flammable and combustible than molded articles from conventional polymer powders.
- the present invention is therefore a powdered composition, in particular building powder or rapid prototyping and rapid-manufacturing powder (RP / RM powder) for rapid prototyping or rapid-manufacturing applications, for processing in a process for layered construction of three-dimensional objects, in which parts of the powder are selectively joined together, which is characterized in that the powder comprises at least one polymer and at least one ammonium polyphosphate flame retardant and a maximum particle size of ⁇ 150 microns.
- RP / RM powder rapid prototyping and rapid-manufacturing powder
- pulverulent composition which is characterized in that a pulverulent mixture of a polymer and a flame retardant comprising ammonium polyphosphate is prepared.
- the present invention is the use of powder according to the invention for the production of moldings by layered and selectively connecting the powder process and moldings, produced by a method for the layered construction of three-dimensional objects, in which parts of a powder are selectively joined together, and which characterized in that they comprise at least one ammonium polyphosphate flame retardant and at least one polymer.
- the powder according to the invention has the advantage that from it by a RP or RM method as described above for the layered construction of three-dimensional objects, in which parts of the powder used are selectively connected to each other, moldings can be produced which have a poorer flammability and flammability exhibit. At the same time, the mechanical properties of the moldings are substantially retained. This opens up areas of application that were previously not possible due to the poor classification of flammability. It was particularly surprising that compliance with minimum levels of ammonium polyphosphate flame retardant in the powders, even a classification of the finished molded article in the V0 level according to UL94 (Underwriters Laboratories Inc, test method 94V) can be achieved.
- molded articles produced from the powder according to the invention have consistently good or even improved mechanical properties, in particular with regard to increased modulus of elasticity, tensile strength and density.
- the appearance of the moldings shows a good quality, for example, a good dimensional stability and surface quality.
- the building powder according to the invention or the powdery composition according to the invention for processing in a layered construction of three-dimensional objects, in which parts of the powder are selectively joined together is characterized in that the powder comprises at least one polymer and at least one flameproofing agent comprising ammonium polyphosphate maximum particle size of ⁇ 150 microns, preferably from 20 to 100 microns.
- the powder is preferably connected by introduction of energy, more preferably by the action of heat, whereby the particles are joined to one another by fusing or sintering.
- the powder can be used in processes in which the particles are connected by chemical reaction with one another or with a binder or by physical measures, preferably drying or adhesive bonding. Details of each procedure can be taken from the above-mentioned documents.
- the polymer and also the flame retardant may be present in the powder according to the invention as a mixture of the respective powders, or as powders in which the majority of the grains or each grain comprises both polymer and flame retardant.
- the flame retardant can be homogeneously distributed in the particles or be enriched in the middle of the particle or on the surface of the particle.
- the powder preferably has as polymer a homo- or copolymer selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, poly (N-methylmethacrylimide) (PMMI), polymethyl methacrylate (PMMA), ionomer, polyamide, copolyester, copolyamides Terpolymers, acrylonitrile-butadiene-styrene copolymers (ABS) or mixtures thereof.
- the powder according to the invention particularly preferably has a polymer which has a melting point of from 50 to 350.degree. C., preferably from 70 to 200.degree.
- the polymers present in the powder according to the invention can be prepared in particular by milling, precipitation and / or anionic polymerization or a combination thereof or by subsequent fractionation.
- the powder according to the invention preferably has, especially when the powder is to be used for selective laser sintering, at least one polyamide.
- the powder according to the invention preferably has a polyamide which has at least 8 carbon atoms per carbonamide group.
- the powder according to the invention preferably has at least one polyamide which has 9 or more carbon atoms per carbonamide group.
- the powder comprises at least one polyamide selected from polyamide 612 (PA 612), polyamide 11 (PA 11) and polyamide 12 (PA 12) or copolyamides based on the aforementioned polyamides.
- the powder according to the invention preferably has an unregulated polyamide.
- a polyamide 12 sintered powder is suitable, which is a Melting temperature of 185 to 189 ° C, preferably from 186 to 188 ° C, a melting enthalpy of 112 ⁇ 17 J / g, preferably from 100 to 125 J / g and a solidification temperature of 133 to 148 ° C, preferably from 139 to 143 ° C has.
- the process for the preparation of the polyamide powder on which the sintering powders according to the invention are based is well known and can be used in the case of PA 12, for example, the documents DE 29 06 647 . DE 35 10 687 .
- polyamide 12 granules is offered by Degussa AG under the trade name VESTAMID.
- polyamide 12 which has a melting temperature of 185 to 189 ° C, preferably from 186 to 188 ° C, a melting enthalpy of 120 ⁇ 17 J / g, preferably from 110 to 130 J / g and a solidification temperature of 130 to 140 ° C, preferably from 135 to 138 ° C and preferably also has a crystallization temperature after aging of 135 to 140 ° C. The determination of these measured values took place as in EP 0 911 142 described by DSC.
- a powder which comprises a copolymer, in particular a copolyamide is particularly suitable.
- the powder according to the invention based on the sum of the polymers present in the powder, preferably contains from 5 to 50% by mass of an ammonium polyphosphate flame retardant, preferably from 10 to 40% by mass of an ammonium polyphosphate flame retardant, more preferably from 20 to 35% by mass of an ammonium polyphosphate Flame retardant and most preferably from 23 to 34% by mass of an ammonium polyphosphate flame retardant, to the specified ranges refer to the total content of ammoniumpolyphosphat ambience in the powder, wherein powder is meant the entire amount consisting of components.
- the powder according to the invention may comprise a mixture of a flame retardant containing ammonium polyphosphate and polymer particles, or else polymer particles or powder having incorporated ammonium polyphosphate flame retardant.
- a proportion of ammonium polyphosphate flame retardant of less than 5 mass% based on the total amount of components the desired effect of the flame retardancy and non-combustibility decreases significantly.
- a proportion of a ammonium polyphosphate flame retardant of more than 50% by mass, based on the total amount of components the mechanical properties such as e.g. the elongation at break of the molded articles produced from such powders clearly.
- the polymer particles have a maximum particle size of 150 ⁇ m, preferably an average particle size of 20 to 100 ⁇ m and more preferably of 45 to 80 ⁇ m.
- the ammonium polyphosphate flame retardant preferably has a particle size which falls below the mean particle size d 50 of the polymer particles or powder by at least 20%, preferably by more than 50% and most preferably by more than 70%.
- the flame retardant component has an average particle size of from 1 to 50 ⁇ m, preferably from 5 to 15 ⁇ m. Due to the small particle size, there is a good distribution of the powdered flame retardant in the powdery polymer powder.
- the flame retardants contained in the powder according to the invention have ammonium polyphosphate as the main component.
- the phosphorus content in the ammonium polyphosphate is preferably from 10 to 35% by mass, preferably from 15 to 32% by mass and very particularly preferably from 20 to 32% by mass.
- the flame retardant is preferably halogen-free. However, it may have synergists, for example carbon formers such as polyalcohols or pentaerythritol, and / or for example an intumescent (intumescent) component such as melamine.
- sulfur can be included in the composition.
- the flame retardant, when in powder form, may further comprise a coating, for compatibilization or to reduce the susceptibility to moisture of the ammonium polyphosphate have. Such coated flame retardants are available, for example, from Budenheim Iberica under the name Budit.
- ammonium polyphosphate flame retardants in general are Budit 3076 DCD or Budit 3076 DCD-2000 from Budenheim Iberica, or products of the Exolit AP series, for example Exolit AP 750 or Exolit AP 422 from Clariant.
- Powder according to the invention may also comprise at least one adjuvant, at least one filler and / or at least one pigment.
- auxiliaries may be, for example, flow aids, such as, for example, fumed silica or precipitated silica. Pyrogenic silica (fumed silica) is offered, for example, under the product name Aerosil ®, with various specifications by Degussa AG.
- the flow aids may be hydrophobic flow aids.
- powder according to the invention has less than 3% by mass, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass of such auxiliaries, based on the total sum of the components, ie the sum of polymers and flame retardants.
- the fillers may be, for example, glass, metal, in particular aluminum or ceramic particles, such as, for example, solid or hollow glass spheres, steel spheres, aluminum spheres or metal semolina or even colored pigments, such as, for example, transition metal oxides.
- the filler particles preferably have a smaller or approximately the same size as the particle size of the polymers.
- the average particle size d 50 of the fillers should not exceed the average particle size d 50 of the polymers by more than 20%, preferably by not more than 15% and most preferably by not more than 5%.
- the particle size is in particular limited by the permissible construction height or layer thickness in the layered apparatus used in each case.
- powder according to the invention has less than 70% by mass, preferably from 0.001 to 60% by mass, particularly preferably from 0.05 to 50% by mass and very particularly preferably from 0.5 to 25% by mass of such fillers, based on the total of the Components so that the volume fraction of the polymers in each case is greater than 50%.
- the preparation of the powders according to the invention is easily possible and is preferably carried out according to the process according to the invention for producing powder according to the invention, which is characterized in that at least one polymer is mixed with at least one flame retardant comprising ammonium polyphosphate.
- Mixing can be done dry in the dry blend.
- a polymer powder obtained, for example, by reprecipitation and / or grinding, which can also be fractionated subsequently, is mixed with the flame retardant comprising ammonium polyphosphate.
- a flow aid for example from the Aerosil R series of Degussa, z.
- the flame retardant comprising ammonium polyphosphate can be compounded into a melt of at least one polymer and the mixture obtained can be processed by grinding into powder.
- the processing of ammonium polyphosphate-based flame retardants in compounding is described, for example, in US Pat Plastics Additives & Compounding, April 2002, Elsevier Advanced Technology, pages 28-33 described.
- a finely divided mixing can be carried out in the simplest embodiment of the method according to the invention, for example by mixing finely powdered flame retardant on the dry powder in high-speed mechanical mixers.
- the powder can be a polymer powder which is already suitable for the layer-wise rapid prototyping process and to which finely divided particles of the flame retardant are simply added.
- the particles preferably have a smaller to at most approximately equal size average particle size as the particles of the polymers.
- the middle should Grain size d 50 of the flame retardant particles, the average particle size d 50 of the polymer powder by more than 20%, preferably by more than 50% and most preferably by more than 70%.
- the grain size is limited to the top in particular by the allowable height or layer thickness in the rapid prototyping system.
- the flame retardant is mixed with a, preferably molten polymer by compounding and the resulting flame retardant-containing polymer is processed by (cold) grinding and optionally fractionation to powder according to the invention.
- a granulate is obtained, which is subsequently processed into powder. This reworking can e.g. by grinding.
- the process variant in which the flame retardant is compounded has the advantage over the pure mixing process that a more homogeneous distribution of the flame retardant in the powder is achieved.
- a suitable flow aid such as fumed alumina, fumed silica or pyrogenic titanium dioxide
- the precipitated or cold-ground powder are added externally.
- a leveling agent such as metal soaps, preferably alkali metal or alkaline earth metal salts of the underlying alkanemonocarboxylic acids or dimer acids, may be added to the precipitated or cold-ground powder.
- the metal soaps were used in amounts of from 0.01 to 30% by weight, preferably 0.5 to 15% by weight, based on the sum of the polyamides present in the powder.
- metal soaps it is preferred to use the sodium or calcium salts of the basic alkane monocarboxylic acids or dimer acids. Examples of commercially available products are Licomont NaV or Licomont CaV from Clariant.
- the metal soap particles can be incorporated into the polyamide particles, but there may also be mixtures of finely divided metal soap particles and polyamide particles.
- inorganic pigments in particular colored pigments, such as e.g. Transition metal oxides, stabilizers, e.g. Phenols, in particular sterically hindered phenols, flow and flow aids, such. fumed silicas and filler particles are added.
- colored pigments such as e.g. Transition metal oxides
- stabilizers e.g. Phenols, in particular sterically hindered phenols
- flow and flow aids such. fumed silicas and filler particles are added.
- concentrations for fillers and / or auxiliaries stated for the powder according to the invention are maintained.
- the present invention also provides the use of powder according to the invention for the production of moldings in a layer-wise and selectively powder-joining (rapid-prototyping or rapid-manufacturing) process, in which powders according to the invention, the polymer and a flame retardant comprising ammonium polyphosphate, preferably each in particulate form, are used.
- the present invention relates to the use of the powder for the production of moldings by selective laser sintering of a flame retardant-containing precipitation powder based on a polyamide 12, which has a melting temperature of 185 to 189 ° C, a melting enthalpy of 112 ⁇ 17 J / g and a solidification temperature of 136 to 145 ° C and its use in US 6,245,281 is described.
- the laser-sintering processes are well known and rely on the selective sintering of polymer particles wherein layers of polymer particles are exposed briefly to laser light, thus bonding the polymer particles exposed to the laser light.
- the successive sintering of layers of polymer particles produces three-dimensional objects. Details of the method of selective laser sintering are eg the fonts US 6,136,948 and WO 96/06881 refer to.
- the powder according to the invention can also be used in other rapid prototyping or rapid manufacturing processes of the prior art, in particular those described above.
- the powder according to the invention can be used in particular for the production of shaped bodies from powders by the SLS process (selective laser sintering), as in US Pat US 6,136,948 or WO 96/06881 described by the SIV method (selectively inhibiting the binding of powder) as in WO 01/38061 described through 3D printing, as in EP 0 431 924 described, or by a microwave method, as in DE 103 11 438 described, are used.
- SLS process selective laser sintering
- SIV method selective inhibiting the binding of powder
- WO 01/38061 described through 3D printing
- EP 0 431 924 described as in EP 0 431 924 described
- a microwave method as in DE 103 11 438 described
- the sensitivity of the flame retardant to air is recommended. In particular, the prolonged contact of the powder according to the invention with air or atmospheric moisture is to be avoided.
- the sensitivity of the powder according to the invention can be reduced, so that a reduction of the modulus of elasticity, which is optionally caused by the decomposition products of ammonium polyphosphate, can be avoided.
- the shaped bodies according to the invention produced by a process for the layered construction of three-dimensional objects, in which parts of a powder, in particular of the powder according to the invention, are interconnected selectively, such as selective laser sintering, are characterized in that they contain at least one ammonium polyphosphate flame retardant and at least one polymer or consist of at least one ammonium polyphosphate flame retardant and at least one polymer.
- the shaped bodies according to the invention preferably have at least one polyamide which has at least 8 carbon atoms per carbonamide group. Very particular preference is given to moldings according to the invention comprising at least one polyamide 612, polyamide 11 and / or a polyamide 12 or copolyamides based on these polyamides and at least one flame retardant comprising ammonium polyphosphate.
- the flame retardant present in the molding according to the invention is based on ammonium polyphosphate.
- the shaped body according to the invention based on the sum of the components present in the molding, of from 5 to 50% by mass of ammoniumpolyphosphat Vietnamese flame retardant, preferably from 10 to 40% by mass, more preferably from 20 to 35 mass% and most preferably from 23 to 34% by mass.
- the maximum amount of ammonium polyphosphate flame retardant is preferably 50% by mass, based on the sum of the components present in the molding.
- the molding has, based on the sum of the existing polymers on 30- 35 wt .-% ammonium polyphosphate having flame retardants.
- the shaped articles may also contain fillers and / or auxiliaries and / or pigments, such as e.g. thermal stabilizers and / or oxidation stabilizers, e.g. have sterically hindered phenol derivatives.
- Fillers may e.g. Glass, ceramic particles and metal particles such as iron balls, or corresponding hollow balls be.
- the shaped bodies according to the invention preferably have glass particles, very particularly preferably glass spheres.
- moldings according to the invention have less than 3% by weight, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass, of such auxiliaries, based on the sum of the components present.
- moldings according to the invention preferably comprise less than 75% by mass, preferably from 0.001 to 70% by mass, more preferably from 0.05 to 50% by mass, and very particularly preferably from 0.5 to 25% by mass of such fillers, based on Sum of existing components.
- the determination of the BET surface area carried out in the following examples was carried out according to DIN 66 131.
- the bulk density was determined using an apparatus according to DIN 53 466.
- the laser diffraction measurements were taken on a Malvem Mastersizer S, Ver. 2.18 received.
- Example 1 Comparative Example (not according to the invention):
- the jacket temperature 2 K - 3 K is kept below the internal temperature.
- the internal temperature is brought to 117 ° C. at the same cooling rate and then kept constant for 60 minutes. Thereafter, the internal temperature is brought to 111 ° C at a cooling rate of 40 K / h. At this temperature, the precipitation begins, recognizable by the development of heat. After 25 minutes, the internal temperature drops, indicating the end of the precipitation.
- the suspension is transferred to a paddle dryer.
- the ethanol is distilled off therefrom while the agitator is running at 70 ° C./400 mbar, and the residue is subsequently dried at 20 mbar / 85 ° C. for 3 hours.
- BET 6.9 m 2 / g Bulk density: 429 g / l
- Example 1 with a mean particle diameter d 50 of 56 microns (laser diffraction) and a bulk density according to DIN 53 466 of 459 g / l is 1023 g (35 parts) of Budit 3076 DCD-2000 in a dry blend method using a Henschel mixer FML10 / KM23 mixed at 700 rpm at 50 ° C in 3 minutes. Subsequently, 1.5 g of Aerosil R 812 (0.05 part) were mixed in at room temperature and 500 rpm in 3 minutes.
- Example 1 with a mean particle diameter d 50 of 56 microns (laser diffraction) and a bulk density according to DIN 53 466 of 459 g / l is 814 g (30 parts) of Budit 3076 DCD in the dry blend method using a Henschel mixer FML10 / KM23 mixed at 700 rpm at 50 ° C in 3 minutes. Subsequently, 54 g (2 parts) of Licomont NaV and 2 g of Aerosil 200 (0.1 part) were mixed in at room temperature and 500 rpm for 3 minutes.
- Example 1 To 1900 g (80 parts) of polyamide 12 powder prepared according to DE 29 06 647 , Example 1 with a mean particle diameter d 50 of 56 microns (laser diffraction) and a bulk density according to DIN 53 466 of 459 g / l 475 g (20 parts) Exolit AP 422 in a dry blend method using a Henschel mixer FML10 / KM23 mixed at 700 rpm at 50 ° C in 3 minutes. Subsequently, 2.4 g of Aerosil 200 (0.1 parts) were mixed in at room temperature and 500 rpm for 3 minutes.
- the powders of Examples 1 to 4 were installed on a laser sintering machine to bars for the fire test UL94V and multi-purpose bars according to ISO 3167. Mechanical values were determined on the latter components by means of a tensile test according to EN ISO 527 (Table 1). The UL bars were used for the UL94V vertical burn test (Underwriters Laboratories Inc.). The bars have the nominal dimensions 3.2 * 10 * 80 mm. The production took place in each case on a laser sintering machine EOSINT P360 of the company EOS GmbH.
- Table 1 Test results of the samples according to Examples 1 to 3 Examples Sample thickness [mm] Modulus N / mm 2 UL total burn time [s] UL classification Shaped body of material from Example 1 3.9 1688 > 167 kE Shaped body of material from Example 2 3.6 1890 19 V0 Shaped article of Example 4 30% Budit 3076 DCD-2000 3.6 1860 11 V0 Shaped body of material from Example 3 30% Budit 3076 DCD-2000 3.6 1885 10 V0 Shaped body of material from Example 3 35% Budit 3076 DCD-2000 3.6 2031 9 V0 Shaped body of material from Example 5 30% Exolit AP 422 3.7 2313 10 V0 Shaped body of material from Example 5 20% Exolit AP 422 3.7 2207 10 V0 (kE: A grading in one of the stages V0 to V2 was not possible.) The bars are thicker than the nominal thickness, which is due to the z-compensation (the laser beam reaches more than one layer thickness, since he also has to reach the layer
- ammonium polyphosphate-based flame retardant to the polymer powder makes it possible to produce moldings which have a significantly better UL classification.
- the flame retardant In addition, an increase in the modulus of elasticity and the tensile strength is achieved, but at the same time the elongation at break is reduced.
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Abstract
Description
Die Erfindung betrifft ein Polymerpulver, welches zumindest ein Polymer und zumindest ein ammoniumpolyphosphathaltiges Flammschutzmittel aufweist, ein Verfahren zur Herstellung dieses Pulvers sowie Formkörper, hergestellt durch schichtweise Auftragung und Verschmelzung dieses Pulvers.The invention relates to a polymer powder which comprises at least one polymer and at least one flame retardant containing ammonium polyphosphate, a process for the preparation of this powder and moldings produced by layered application and fusion of this powder.
Die zügige Bereitstellung von Prototypen ist eine in der jüngsten Zeit häufig gestellte Aufgabe. Dabei sind aufgrund ihrer Flexibilität besonders die Verfahren im Fokus, die ein pulverförmiges Material schichtweise auftragen und selektiv schmelzen oder verbinden.The speedy provision of prototypes is a common task in recent times. Due to their flexibility, the focus is particularly on the processes which apply a powdered material in layers and selectively melt or join.
Ein Verfahren, welches besonders gut für den Zweck des Rapid Prototypings geeignet ist, ist das selektive Laser-Sintern. Bei diesem Verfahren werden Kunststoffpulver in einer Kammer selektiv kurz mit einem Laserstrahl belichtet, wodurch die Pulver-Partikel, die von dem Laserstrahl getroffen werden, schmelzen. Die geschmolzenen Partikel verlaufen ineinander und erstarren schnell wieder zu einer festen Masse. Durch wiederholtes Belichten von immer neu aufgebrachten Schichten können mit diesem Verfahren dreidimensionale Körper auch komplexer Geometrie einfach und schnell hergestellt werden.One method which is particularly well suited for the purpose of rapid prototyping is selective laser sintering. In this method, plastic powders in a chamber are selectively exposed to a short laser beam, thereby melting the powder particles that are hit by the laser beam. The molten particles run into each other and solidify quickly back to a solid mass. By repeatedly exposing layers that are always newly applied, three-dimensional bodies of even complex geometry can be produced easily and quickly with this method.
Das Verfahren des Laser-Sinterns (Rapid Prototyping) zur Darstellung von Formkörpern aus pulverförmigen Polymeren wird ausführlich in den Schriften
In der Praxis hat sich beim Laser-Sintern vor allem Polyamid 12-Pulver (PA 12) für die Herstellung von Formkörpern, insbesondere von technischen Bauteilen bewährt. Die aus PA-12 Pulver gefertigten Teile genügen den hohen Anforderungen, die bezüglich der mechanischen Beanspruchung gestellt werden und kommen damit in ihren Eigenschaften besonders nahe an die späteren Serienteile, die durch Extrusion oder Spritzgießen erstellt werden.In practice, especially polyamide 12 powder (PA 12) has proven successful in the production of molded articles, in particular of technical components during laser sintering. Made of PA-12 powder, the parts meet the high demands that are placed on the mechanical stress and thus come in their properties particularly close to the later series parts, created by extrusion or injection molding become.
Gut geeignet ist dabei ein PA 12-Pulver mit einer mittleren Korngröße (d50) von 50 bis 150 µm, wie man es beispielsweise gemäß
Andere gut geeignete Verfahren sind das SIV-Verfahren, wie es in
Für die genannten Rapid-Prototyping- bzw. Rapid-Manufacturing-Verfahren (RP- oder RM-Verfahren) können pulverförmige Substrate, insbesondere Polymere oder Copolymere, vorzugsweise ausgewählt aus Polyester, Polyvinylchlorid, Polyacetal, Polypropylen, Polyethylen, Polystyrol, Polycarbonat, Poly-(N-methylmethacrylimide) (PMMI), Polymethylmethacrylat (PMMA), lonomer, Polyamid, Copolyester, Copolyamide, Terpolymere, Acrylnitril-Butadien-Styrol-Copolymere (ABS) oder Gemische davon eingesetzt werden.For the abovementioned rapid prototyping or rapid manufacturing processes (RP or RM processes) it is possible to use pulverulent substrates, in particular polymers or copolymers, preferably selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, polypropylene (N-methylmethacrylimide) (PMMI), polymethylmethacrylate (PMMA), ionomer, polyamide, copolyesters, copolyamides, terpolymers, acrylonitrile-butadiene-styrene copolymers (ABS) or mixtures thereof.
Trotz der bereits guten Eigenschaften der bekannten Polymerpulver weisen mit solchen Pulvern hergestellte Formkörper noch immer einige Nachteile auf. Nachteilig bei den derzeit eingesetzten Polymerpulvern sind insbesondere ihre leichte Entflamm- und Brennbarkeit. Das verhindert derzeit den Einsatz oben beschriebener Verfahren für den Einsatz in Kleinserien beispielsweise im Flugzeugbau.
Aufgabe der vorliegenden Erfindung war es deshalb, ein Polymerpulver bereitzustellen, welches eine schlechtere Entflammbarkeit der daraus mit einem der oben beschriebenen Verfahren hergestellten Teile ermöglicht.Despite the already good properties of the known polymer powders, molded articles produced with such powders still have some disadvantages. A disadvantage of the polymer powders currently used are in particular their ease of ignition and flammability. This currently prevents the use of the above-described methods for use in small batches, for example in aircraft construction.
The object of the present invention was therefore to provide a polymer powder, which allows for less flammability of the parts made therefrom with any of the methods described above.
Überraschenderweise wurde nun, wie in den Ansprüchen beschrieben, gefunden, dass sich durch Zugabe von ammoniumpolyphosphathaltigen Flammschutzmitteln zu Polymeren oder Copolymeren pulverförmige Kompositionen (Pulver) herstellen lassen, aus denen sich Formkörper durch ein schichtweise arbeitendes Verfahren, bei dem selektiv Bereiche aufgeschmolzen oder miteinander verbunden werden, produzieren lassen, die deutlich schlechter entflammbar und brennbar sind als Formkörper aus herkömmlichen Polymerpulvern.Surprisingly, it has now been found, as described in the claims, that pulverulent compositions (powders) can be prepared by adding ammoniumpolyphosphate flame retardants to polymers or copolymers, from which moldings are melted by a layer-by-layer process in which areas are selectively melted or bonded together , can produce, which are significantly less flammable and combustible than molded articles from conventional polymer powders.
Gegenstand der vorliegenden Erfindung ist deshalb eine pulverförmige Zusammensetzung, insbesondere Baupulver bzw. Rapid-Prototyping- und Rapid-Manufacturing-Pulver (RP-/RM-Pulver) für Rapid-Prototyping- oder Rapid-Manufacturing-Anwendungen, zur Verarbeitung in einem Verfahren zum schichtweisen Aufbau von dreidimensionalen Gegenständen, bei dem selektiv Teile des Pulvers miteinander verbunden werden, die dadurch gekennzeichnet ist, dass das Pulver zumindest ein Polymer und zumindest ein Ammoniumpolyphosphat aufweisendes Flammschutzmittel und eine maximale Partikelgröße von ≤ 150 µm aufweist.The present invention is therefore a powdered composition, in particular building powder or rapid prototyping and rapid-manufacturing powder (RP / RM powder) for rapid prototyping or rapid-manufacturing applications, for processing in a process for layered construction of three-dimensional objects, in which parts of the powder are selectively joined together, which is characterized in that the powder comprises at least one polymer and at least one ammonium polyphosphate flame retardant and a maximum particle size of ≤ 150 microns.
Ebenso ist Gegenstand der vorliegenden Erfindung ein Verfahren zur Herstellung von erfindungsgemäßem Pulver (pulverförmiger Komposition), welches dadurch gekennzeichnet ist, dass eine pulverförmige Mischung eines Polymeren und eines Ammoniumpolyphosphat aufweisenden Flammschutzmittels hergestellt wird.Likewise provided by the present invention is a process for producing powder according to the invention (pulverulent composition), which is characterized in that a pulverulent mixture of a polymer and a flame retardant comprising ammonium polyphosphate is prepared.
Außerdem ist Gegenstand der vorliegenden Erfindung die Verwendung von erfindungsgemäßem Pulver zur Herstellung von Formkörpern durch schichtweise arbeitende und selektiv das Pulver verbindende Verfahren sowie Formkörper, hergestellt durch ein Verfahren zum schichtweisen Aufbau von dreidimensionalen Gegenständen, bei dem selektiv Teile eines Pulvers miteinander verbunden werden, und welche dadurch gekennzeichnet sind, dass sie zumindest ein Ammoniumpolyphosphat aufweisendes Flammschutzmittel und zumindest ein Polymer aufweisen.In addition, the present invention is the use of powder according to the invention for the production of moldings by layered and selectively connecting the powder process and moldings, produced by a method for the layered construction of three-dimensional objects, in which parts of a powder are selectively joined together, and which characterized in that they comprise at least one ammonium polyphosphate flame retardant and at least one polymer.
Das erfindungsgemäße Pulver hat den Vorteil, dass aus ihm durch ein wie oben beschriebenes RP- oder RM-Verfahren zum schichtweisen Aufbau von dreidimensionalen Gegenständen, bei dem selektiv Teile des eingesetzten Pulvers miteinander verbunden werden, Formkörper hergestellt werden können, die eine schlechtere Brennbarkeit und Entflammbarkeit aufweisen. Gleichzeitig werden die mechanischen Eigenschaften der Formkörper im wesentlichen beibehalten. Damit eröffnen sich Anwendungsbereiche, die bisher aufgrund der schlechten Einstufung, was die Brennbarkeit angeht, nicht möglich waren. Besonders überraschend war, dass bei Einhaltung von Mindestgehalten an Ammoniumpolyphosphat aufweisendem Flammschutzmittel in den Pulvern, sogar eine Einstufung des fertigen Formkörpers in die Stufe V0 gemäß UL94 (Underwriters Laboratories Inc, Testverfahren 94V) erreicht werden kann.The powder according to the invention has the advantage that from it by a RP or RM method as described above for the layered construction of three-dimensional objects, in which parts of the powder used are selectively connected to each other, moldings can be produced which have a poorer flammability and flammability exhibit. At the same time, the mechanical properties of the moldings are substantially retained. This opens up areas of application that were previously not possible due to the poor classification of flammability. It was particularly surprising that compliance with minimum levels of ammonium polyphosphate flame retardant in the powders, even a classification of the finished molded article in the V0 level according to UL94 (Underwriters Laboratories Inc, test method 94V) can be achieved.
Außerdem konnte überraschenderweise festgestellt werden, dass Formkörper, hergestellt aus dem erfindungsgemäßen Pulver, gleichbleibend gute oder sogar verbesserte mechanische Eigenschaften aufweisen, insbesondere hinsichtlich erhöhtem Elastizitätsmodul, Zugfestigkeit und Dichte. Auch das Aussehen der Formkörper zeigt eine gute Qualität, beispielsweise eine gute Maßhaltigkeit und Oberflächengüte.In addition, it has surprisingly been found that molded articles produced from the powder according to the invention have consistently good or even improved mechanical properties, in particular with regard to increased modulus of elasticity, tensile strength and density. The appearance of the moldings shows a good quality, for example, a good dimensional stability and surface quality.
Das erfindungsgemäße Pulver sowie ein Verfahren zu dessen Herstellung wird nachfolgend beschrieben, ohne dass die Erfindung darauf beschränkt sein soll.The powder according to the invention and a process for its preparation is described below, without the invention being restricted thereto.
Das erfindungsgemäße Baupulver bzw. die erfindungsgemäße pulverförmige Zusammensetzung zur Verarbeitung in einem Verfahren zum schichtweisen Aufbau von dreidimensionalen Gegenständen, bei dem selektiv Teile des Pulvers miteinander verbunden werden, zeichnet sich dadurch aus, dass das Pulver zumindest ein Polymer und zumindest ein Ammoniumpolyphosphat aufweisendes Flammschutzmittel und eine maximale Partikelgröße von ≤ 150 µm, vorzugsweise von 20 bis 100 µm aufweist. Das Pulver wird in diesen Verfahren vorzugsweise durch Energieeintrag, besonders bevorzugt durch Wärmeeinwirkung, verbunden, wobei die Partikel untereinander durch verschmelzen oder versintern verbunden werden. Ebenso ist das Pulver einsetzbar in Verfahren, bei denen die Partikel durch chemische Reaktion untereinander oder mit einem Binder oder durch physikalische Maßnahmen, bevorzugt Trocknung oder Verklebung verbunden werden. Details zu den einzelnen Verfahren können den oben genannten Schriften entnommen werden.The building powder according to the invention or the powdery composition according to the invention for processing in a layered construction of three-dimensional objects, in which parts of the powder are selectively joined together, is characterized in that the powder comprises at least one polymer and at least one flameproofing agent comprising ammonium polyphosphate maximum particle size of ≤ 150 microns, preferably from 20 to 100 microns. In this process, the powder is preferably connected by introduction of energy, more preferably by the action of heat, whereby the particles are joined to one another by fusing or sintering. Likewise, the powder can be used in processes in which the particles are connected by chemical reaction with one another or with a binder or by physical measures, preferably drying or adhesive bonding. Details of each procedure can be taken from the above-mentioned documents.
Das Polymer und auch das Flammschutzmittel können in dem erfindungsgemäßen Pulver als Mischung der jeweiligen Pulver vorliegen, oder als Pulver, in denen die überwiegende Anzahl der Körner oder jedes Korn sowohl Polymer als auch Flammschutzmittel aufweist. Bei solchen Pulvern kann das Flammschutzmittel homogen in den Partikeln verteilt sein oder aber in der Mitte des Partikels oder an der Oberfläche des Partikels angereichert sein.The polymer and also the flame retardant may be present in the powder according to the invention as a mixture of the respective powders, or as powders in which the majority of the grains or each grain comprises both polymer and flame retardant. In such powders, the flame retardant can be homogeneously distributed in the particles or be enriched in the middle of the particle or on the surface of the particle.
Das Pulver weist als Polymer vorzugsweise ein Homo- oder Copolymer ausgewählt aus Polyester, Polyvinylchlorid, Polyacetal, Polypropylen, Polyethylen, Polystyrol, Polycarbonat, Poly-(N-methylmethacrylimide) (PMMI), Polymethylmethacrylat (PMMA), lonomer, Polyamid, Copolyester, Copolyamide, Terpolymere, Acrylnitril-Butadien-Styrol-Copolymere (ABS) oder Gemischen davon aus. Besonders bevorzugt weist das erfindungsgemäße Pulver ein Polymer auf, welches eine Schmelztemperatur von 50 bis 350 °C, vorzugsweise von 70 bis 200 °C aufweist.The powder preferably has as polymer a homo- or copolymer selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, poly (N-methylmethacrylimide) (PMMI), polymethyl methacrylate (PMMA), ionomer, polyamide, copolyester, copolyamides Terpolymers, acrylonitrile-butadiene-styrene copolymers (ABS) or mixtures thereof. The powder according to the invention particularly preferably has a polymer which has a melting point of from 50 to 350.degree. C., preferably from 70 to 200.degree.
Die im erfindungsgemäßen Pulver vorhandenen Polymere können insbesondere durch Vermahlen, Fällen und/oder anionische Polymerisation oder einer Kombination daraus oder durch anschließende Fraktionierung hergestellt werden.The polymers present in the powder according to the invention can be prepared in particular by milling, precipitation and / or anionic polymerization or a combination thereof or by subsequent fractionation.
Das erfindungsgemäße Pulver weist vorzugsweise, insbesondere wenn das Pulver zum selektiven Laser-Sintern eingesetzt werden soll, zumindest ein Polyamid auf. Als Polyamid weist das erfindungsgemäße Pulver vorzugsweise ein Polyamid auf, welches pro Carbonamid-Gruppe mindestens 8 Kohlenstoffatome aufweist. Bevorzugt weist das erfindungsgemäße Pulver mindestens ein Polyamid auf, welches 9 oder mehr Kohlenstoffatome pro Carbonamid-Gruppe aufweist. Ganz besonders bevorzugt weist das Pulver zumindest ein Polyamid, ausgewählt aus Polyamid 612 (PA 612), Polyamid 11 (PA 11) und Polyamid 12 (PA 12) oder Copolyamide, basierend auf den vorgenannten Polyamiden, auf. Das erfindungsgemäße Pulver weist vorzugsweise ein ungeregeltes Polyamid auf.The powder according to the invention preferably has, especially when the powder is to be used for selective laser sintering, at least one polyamide. As a polyamide, the powder according to the invention preferably has a polyamide which has at least 8 carbon atoms per carbonamide group. The powder according to the invention preferably has at least one polyamide which has 9 or more carbon atoms per carbonamide group. Most preferably, the powder comprises at least one polyamide selected from polyamide 612 (PA 612), polyamide 11 (PA 11) and polyamide 12 (PA 12) or copolyamides based on the aforementioned polyamides. The powder according to the invention preferably has an unregulated polyamide.
Für das Lasersintern ist insbesondere ein Polyamid 12 Sinterpulver geeignet, welches eine Schmelztemperatur von 185 bis 189 °C, vorzugsweise von 186 bis 188 °C, eine Schmelzenthalpie von 112 ± 17 J/g, vorzugsweise von 100 bis 125 J/g und eine Erstarrungstemperatur von 133 bis 148 °C, vorzugsweise von 139 bis 143 °C aufweist. Der Prozess für die Herstellung für die den erfindungsgemäßen Sinterpulvern zugrunde liegenden Polyamidpulver ist allgemein bekannt und kann im Fall von PA 12 z.B. den Schriften
Ebenfalls besonders gut geeignet ist Polyamid 12, welches eine Schmelztemperatur von 185 bis 189 °C, vorzugsweise von 186 bis 188 °C, eine Schmelzenthalpie von 120 ± 17 J/g, vorzugsweise von 110 bis 130 J/g und eine Erstarrungstemperatur von 130 bis 140 °C, vorzugsweise von 135 bis 138 °C und vorzugsweise auch eine Kristallisationstemperatur nach einer Alterung von 135 bis 140 °C aufweist. Die Ermittlung dieser Messwerte erfolgte wie in
Für die nicht mit einem Laser arbeitenden Verfahren zur Herstellung von dreidimensionalen Objekten ist ein Pulver, welches ein Copolymer, insbesondere ein Copolyamid aufweist, besonders gut geeignet.For the non-laser process for producing three-dimensional objects, a powder which comprises a copolymer, in particular a copolyamide, is particularly suitable.
Das erfindungsgemäße Pulver weist bezogen auf die Summe der im Pulver vorhandenen Polymere vorzugsweise von 5 bis 50 Massen-% an einem Ammoniumpolyphosphat aufweisenden Flammschutzmittel, bevorzugt von 10 bis 40 Massen-% eines ammoniumpolyphosphathaltigen Flammschutzmittels, besonders bevorzugt von 20 bis 35 Massen-% eines ammoniumpolyphosphathaltigen Flammschutzmittels und ganz besonders bevorzugt von 23 bis 34 Massen-% eines ammoniumpolyphosphathaltigen Flammschutzmittels, auf Die angegebenen Bereiche beziehen sich dabei auf den Gesamtgehalt eines ammoniumpolyphosphathaltigen Flammschutzmittels im Pulver, wobei mit Pulver die gesamte aus Komponenten bestehende Menge gemeint ist.The powder according to the invention, based on the sum of the polymers present in the powder, preferably contains from 5 to 50% by mass of an ammonium polyphosphate flame retardant, preferably from 10 to 40% by mass of an ammonium polyphosphate flame retardant, more preferably from 20 to 35% by mass of an ammonium polyphosphate Flame retardant and most preferably from 23 to 34% by mass of an ammonium polyphosphate flame retardant, to the specified ranges refer to the total content of ammoniumpolyphosphathaltigen flame retardant in the powder, wherein powder is meant the entire amount consisting of components.
Das erfindungsgemäße Pulver kann eine Mischung eines ammoniumpolyphosphathaltigen Flammschutzmittels und Polymerpartikeln aufweisen oder aber Polymerpartikel bzw. -pulver, welche eingearbeitetes ammoniumpolyphosphathaltiges Flammschutzmittel aufweisen. Bei einem Anteil eines ammoniumpolyphosphathaltigen Flammschutzmittels von unter 5 Massen-% bezogen auf die gesamte aus Komponenten bestehende Menge nimmt der gewünschte Effekt der Schwereentflammbarkeit und Nichtbrennbarkeit deutlich ab. Bei einem Anteil eines ammoniumpolyphosphathaltigen Flammschutzmittels von über 50 Massen-% bezogen auf die gesamte aus Komponenten bestehende Menge verschlechtern sich die mechanischen Eigenschaften wie z.B. die Reißdehnung der aus solchen Pulvern hergestellten Formkörper deutlich.The powder according to the invention may comprise a mixture of a flame retardant containing ammonium polyphosphate and polymer particles, or else polymer particles or powder having incorporated ammonium polyphosphate flame retardant. With a proportion of ammonium polyphosphate flame retardant of less than 5 mass% based on the total amount of components, the desired effect of the flame retardancy and non-combustibility decreases significantly. With a proportion of a ammonium polyphosphate flame retardant of more than 50% by mass, based on the total amount of components, the mechanical properties such as e.g. the elongation at break of the molded articles produced from such powders clearly.
Weist das Pulver eine Mischung von Polymerpartikeln und einem ammoniumpolyphosphathaltigen Flammschutzmittel auf, so weisen die Polymerpartikel eine maximale Partikelgröße von 150 µm, vorzugsweise eine mittlere Partikelgröße von 20 bis 100 µm und besonders bevorzugt von 45 bis 80 µm auf. Das ammoniumpolyphosphathaltige Flammschutzmittel weist vorzugsweise eine Partikelgröße auf, die die mittlere Korngröße d50 der Polymerpartikel bzw. -pulver um mindestens 20 %, vorzugsweise um mehr als 50 % und ganz besonders bevorzugt um mehr als 70 % unterschreiten. Insbesondere weist die Flammschutzkomponente eine mittlere Partikelgröße von 1 bis 50 µm, bevorzugt von 5 bis 15 µm auf. Durch die geringe Partikelgröße kommt es zu einer guten Verteilung des pulverförmigen Flammschutzmittels in dem pulverförmigen Polymerpulver.If the powder has a mixture of polymer particles and an ammonium polyphosphate-containing flame retardant, the polymer particles have a maximum particle size of 150 μm, preferably an average particle size of 20 to 100 μm and more preferably of 45 to 80 μm. The ammonium polyphosphate flame retardant preferably has a particle size which falls below the mean particle size d 50 of the polymer particles or powder by at least 20%, preferably by more than 50% and most preferably by more than 70%. In particular, the flame retardant component has an average particle size of from 1 to 50 μm, preferably from 5 to 15 μm. Due to the small particle size, there is a good distribution of the powdered flame retardant in the powdery polymer powder.
Die im erfindungsgemäßen Pulver enthaltenen Flammschutzmittel weisen Ammoniumpolyphosphat als Hauptkomponente auf. Der Phosphorgehalt im Ammoniumpolyphosphat beträgt dabei bevorzugt von 10 bis 35 Massen-%, bevorzugt 15 bis 32 Massen-% und ganz besonders bevorzugt 20 bis 32 Massen%. Das Flammschutzmittel ist vorzugsweise halogenfrei. Es kann jedoch Synergisten aufweisen, beispielsweise Kohlenstoffbildner wie Polyalkohole oder Pentaerythrit, und/oder beispielsweise eine intumeszierende (aufschäumende) Komponente wie Melamin. Außerdem kann Schwefel in der Komposition enthalten sein. Das Flammschutzmittel kann, wenn es als Pulver vorliegt, ferner ein Coating, zur Verträglichkeitsvermittlung oder um die Feuchtigkeitsanfälligkeit des Ammoniumpolyphosphates zu reduzieren, aufweisen. Solche gecoateten Flammschutzmittel sind beispielsweise bei Budenheim Iberica unter dem Namen Budit erhältlich.The flame retardants contained in the powder according to the invention have ammonium polyphosphate as the main component. The phosphorus content in the ammonium polyphosphate is preferably from 10 to 35% by mass, preferably from 15 to 32% by mass and very particularly preferably from 20 to 32% by mass. The flame retardant is preferably halogen-free. However, it may have synergists, for example carbon formers such as polyalcohols or pentaerythritol, and / or for example an intumescent (intumescent) component such as melamine. In addition, sulfur can be included in the composition. The flame retardant, when in powder form, may further comprise a coating, for compatibilization or to reduce the susceptibility to moisture of the ammonium polyphosphate have. Such coated flame retardants are available, for example, from Budenheim Iberica under the name Budit.
Kommerziell erhältliche Beispiele für Ammoniumpolyphosphat aufweisende Flammschutzmittel im allgemeinen sind Budit 3076 DCD bzw. Budit 3076 DCD-2000 der Firma Budenheim Iberica, oder Produkte der Exolit AP-Reihe, beispielsweise Exolit AP 750 oder Exolit AP 422 von der Firma Clariant.Commercially available examples of ammonium polyphosphate flame retardants in general are Budit 3076 DCD or Budit 3076 DCD-2000 from Budenheim Iberica, or products of the Exolit AP series, for example Exolit AP 750 or Exolit AP 422 from Clariant.
Erfindungsgemäßes Pulver kann außerdem zumindest einen Hilfsstoff, zumindest einen Füllstoff und/oder zumindest ein Pigment aufweisen. Solche Hilfsstoffe können z.B. Rieselhilfsmittel, wie z.B. pyrogenes Siliziumdioxid oder auch gefällte Kieselsäure sein. Pyrogenes Siliziumdioxid (pyrogene Kieselsäure) wird zum Beispiel unter dem Produktnamen Aerosil®, mit unterschiedlichen Spezifikationen, durch die Degussa AG angeboten. Insbesondere können die Rieselhilfsmittel hydrophobe Rieselhilfen sein. Vorzugsweise weist erfindungsgemäßes Pulver weniger als 3 Massen-%, vorzugsweise von 0,001 bis 2 Massen-% und ganz besonders bevorzugt von 0,05 bis 1 Massen-% solcher Hilfsstoffe bezogen auf Gesamtsumme der Komponenten, also der Summe aus Polymeren und Flammschutzmittel auf. Die Füllstoffe können z.B. Glas-, Metall-, insbesondere Aluminium- oder Keramikpartikel, wie z.B. massive oder hohle Glaskugeln, Stahlkugeln, Aluminiumkugeln oder Metallgrieß oder auch Buntpigmente, wie z.B. Übergangsmetalloxide sein.Powder according to the invention may also comprise at least one adjuvant, at least one filler and / or at least one pigment. Such auxiliaries may be, for example, flow aids, such as, for example, fumed silica or precipitated silica. Pyrogenic silica (fumed silica) is offered, for example, under the product name Aerosil ®, with various specifications by Degussa AG. In particular, the flow aids may be hydrophobic flow aids. Preferably, powder according to the invention has less than 3% by mass, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass of such auxiliaries, based on the total sum of the components, ie the sum of polymers and flame retardants. The fillers may be, for example, glass, metal, in particular aluminum or ceramic particles, such as, for example, solid or hollow glass spheres, steel spheres, aluminum spheres or metal semolina or even colored pigments, such as, for example, transition metal oxides.
Die Füllstoffpartikel weisen dabei vorzugsweise eine kleinere oder ungefähr gleich große mittlere Korngröße wie die Partikel der Polymere auf. Vorzugsweise sollte die mittlere Korngröße d50 der Füllstoffe die mittlere Korngröße d50 der Polymere um nicht mehr als 20 %, vorzugsweise um nicht mehr als 15 % und ganz besonders bevorzugt um nicht mehr als 5 % überschreiten. Die Partikelgröße ist insbesondere limitiert durch die zulässige Bauhöhe bzw. Schichtdicke in der jeweils verwendeten schichtweise arbeitenden Apparatur. Vorzugsweise weist erfindungsgemäßes Pulver weniger als 70 Massen-%, bevorzugt von 0,001 bis 60 Massen-%, besonders bevorzugt von 0,05 bis 50 Massen-% und ganz besonders bevorzugt von 0,5 bis 25 Massen-% solcher Füllstoffe bezogen auf die Gesamtsumme der Komponenten auf, so dass der Volumenanteil der Polymere in jedem Fall größer 50 % beträgt.The filler particles preferably have a smaller or approximately the same size as the particle size of the polymers. Preferably, the average particle size d 50 of the fillers should not exceed the average particle size d 50 of the polymers by more than 20%, preferably by not more than 15% and most preferably by not more than 5%. The particle size is in particular limited by the permissible construction height or layer thickness in the layered apparatus used in each case. Preferably, powder according to the invention has less than 70% by mass, preferably from 0.001 to 60% by mass, particularly preferably from 0.05 to 50% by mass and very particularly preferably from 0.5 to 25% by mass of such fillers, based on the total of the Components so that the volume fraction of the polymers in each case is greater than 50%.
Beim Überschreiten der angegebenen Höchstgrenzen für Hilfs- und/oder Füllstoffe kann es, je nach eingesetztem Füll- oder Hilfsstoff zu deutlichen Verschlechterungen der mechanischen Eigenschaften von Formkörpern kommen, die mittels solcher Pulver hergestellt wurden.Exceeding the specified maximum limits for auxiliaries and / or fillers, depending on the filler or auxiliary used, can lead to significant deterioration of the mechanical properties of moldings produced by means of such powders.
Die Herstellung der erfindungsgemäßen Pulver ist einfach möglich und erfolgt bevorzugt gemäß dem erfindungsgemäßen Verfahren zur Herstellung von erfindungsgemäßem Pulver, welches sich dadurch auszeichnet, dass zumindest ein Polymer mit zumindest einem Ammoniumpolyphosphat aufweisendem Flammschutzmittel vermischt wird. Das Mischen kann trocken im Dry Blend erfolgen. Vorzugsweise wird ein z.B. durch Umfällung und/oder Vermahlung erhaltenes Polymerpulver, welches auch noch anschließend fraktioniert werden kann, mit dem Ammoniumpolyphosphat aufweisenden Flammschutzmittel vermischt. Dabei kann es von Vorteil sein, das pulverförmige Flammschutzmittel zunächst allein oder aber auch die fertige Mischung mit einer Rieselhilfe zu versehen, beispielsweise aus der Aerosil-R-Reihe von Degussa, z. B. Aerosil R972 oder R812. In einer anderen Verfahrensvariante kann das Ammoniumpolyphosphat aufweisende Flammschutzmittel in eine Schmelze von zumindest einem Polymer eincompoundiert werden und das erhaltene Gemisch durch Vermahlung zu Pulver verarbeitet werden. Die Verarbeitung von auf Ammoniumpolyphosphat basierenden Flammschutzmitteln beim Compoundieren wird beispielsweise in
Eine feinteilige Vermischung kann in der einfachsten Ausführungsart des erfindungsgemäßen Verfahrens beispielsweise durch Aufmischen fein gepulverten Flammschutzmittels auf das trockene Pulver in schnelllaufenden mechanischen Mischern erfolgen.A finely divided mixing can be carried out in the simplest embodiment of the method according to the invention, for example by mixing finely powdered flame retardant on the dry powder in high-speed mechanical mixers.
Das Pulver kann bei einer dieser ersten Varianten des erfindungsgemäßen Verfahrens ein bereits für die schichtweise arbeitenden Rapid-Prototyping Verfahren geeignetes Polymerpulver sein, dem einfach feinteilige Partikel des Flammschutzmittels zugemischt werden. Die Partikel weisen dabei vorzugsweise eine kleinere bis maximal ungefähr gleich große mittlere Korngröße wie die Partikel der Polymere auf. Vorzugsweise sollte die mittlere Korngröße d50 der Flammschutzpartikel die mittlere Korngröße d50 der Polymerpulver um mehr als 20 %, vorzugsweise um mehr als 50 % und ganz besonders bevorzugt um mehr als 70 % unterschreiten. Die Korngröße ist nach oben hin insbesondere limitiert durch die zulässige Bauhöhe bzw. Schichtdicke in der Rapid-Prototyping-Anlage.In one of these first variants of the process according to the invention, the powder can be a polymer powder which is already suitable for the layer-wise rapid prototyping process and to which finely divided particles of the flame retardant are simply added. The particles preferably have a smaller to at most approximately equal size average particle size as the particles of the polymers. Preferably, the middle should Grain size d 50 of the flame retardant particles, the average particle size d 50 of the polymer powder by more than 20%, preferably by more than 50% and most preferably by more than 70%. The grain size is limited to the top in particular by the allowable height or layer thickness in the rapid prototyping system.
Es ist ebenso möglich, herkömmliche Polymerpulver mit erfindungsgemäßen Pulvern zu mischen. Auf diese Weise lassen sich Pulver mit einer optimalen Kombination von mechanischen und flammhemmenden Eigenschaften herstellen. Das Verfahren zur Herstellung solcher Mischungen kann z.B.
In einer weiteren Verfahrensvariante wird das Flammschutzmittel mit einem, vorzugsweise geschmolzenem Polymer durch Eincompoundieren gemischt und das erhaltene flammschutzmittel-haltige Polymer wird durch (Kalt-)-Mahlung und gegebenenfalls Fraktionierung zu erfindungsgemäßen Pulver verarbeitet. Üblicherweise wird bei der Compoundierung ein Granulat erhalten, welches anschließend zu Pulver verarbeitet wird. Diese Umarbeitung kann z.B. durch Vermahlen erfolgen. Die Verfahrensvariante, bei welcher das Flammschutzmittel eincompoundiert wird, hat gegenüber dem reinen Mischungsverfahren den Vorteil, dass eine homogenere Verteilung des Flammschutzmittels in dem Pulver erzielt wird.In a further process variant, the flame retardant is mixed with a, preferably molten polymer by compounding and the resulting flame retardant-containing polymer is processed by (cold) grinding and optionally fractionation to powder according to the invention. Usually, in the compounding, a granulate is obtained, which is subsequently processed into powder. This reworking can e.g. by grinding. The process variant in which the flame retardant is compounded has the advantage over the pure mixing process that a more homogeneous distribution of the flame retardant in the powder is achieved.
Gegebenenfalls kann zur Verbesserung des Rieselverhaltens dem erfindungsgemäßen Pulver eine geeignete Rieselhilfe, wie pyrogenes Aluminiumoxid, pyrogenes Siliziumdioxid oder pyrogenes Titandioxid, dem gefällten oder kaltgemahlenen Pulver äußerlich zugesetzt werden.Optionally, to improve the flowability of the powder according to the invention a suitable flow aid, such as fumed alumina, fumed silica or pyrogenic titanium dioxide, the precipitated or cold-ground powder are added externally.
Zur Verbesserung des Schmelzeverlaufs bei der Herstellung der Formkörper kann ein Verlaufsmittel wie beispielsweise Metallseifen, bevorzugt Alkali- oder Erdalkalisalze der zugrunde liegenden Alkanmonocarbonsäuren oder Dimersäuren, dem gefällten oder kalt gemahlenen Pulver zugesetzt werden.To improve the melt flow during the production of the moldings, a leveling agent such as metal soaps, preferably alkali metal or alkaline earth metal salts of the underlying alkanemonocarboxylic acids or dimer acids, may be added to the precipitated or cold-ground powder.
Als Flammschutzmittel können handelsübliche Produkte, die beispielsweise bei der Fa. Budenheim Iberica oder Clariant unter dem Handelsnamen Exolit AP® oder Budit® bezogen werden können, bzw. die oben beschriebenen eingesetzt werden.As a flame retardant, commercially available products that can be purchased under the trade name Exolit ® AP or Budit ®, for example at the company. Budenheim Iberica or Clariant, or which are used as described above.
Die Metallseifen wurden in Mengen von 0,01 bis 30 Gew.%, vorzugsweise 0,5 bis 15 Gew.-%, bezogen auf die Summe der im Pulver vorhandenen Polyamide, eingesetzt. Bevorzugt wurden als Metallseifen die Natrium- oder Calciumsalze der zugrundeliegenden Alkanmonocarbonsäuren oder Dimersäuren eingesetzt. Beispiele für kommerziell verfügbare Produkte sind Licomont NaV oder Licomont CaV der Firma Clariant.The metal soaps were used in amounts of from 0.01 to 30% by weight, preferably 0.5 to 15% by weight, based on the sum of the polyamides present in the powder. As metal soaps it is preferred to use the sodium or calcium salts of the basic alkane monocarboxylic acids or dimer acids. Examples of commercially available products are Licomont NaV or Licomont CaV from Clariant.
Die Metallseifenpartikel können in die Polyamidpartikel eingearbeitet werden, es können aber auch Mischungen von feinteiligen Metallseifenpartikeln und Polyamidpartikeln vorliegen.The metal soap particles can be incorporated into the polyamide particles, but there may also be mixtures of finely divided metal soap particles and polyamide particles.
Zur Verbesserung der Verarbeitungsfähigkeit oder zur weiteren Modifikation des Pulvers können diesem anorganische Pigmente, insbesondere Buntpigmente, wie z.B. Übergangsmetalloxide, Stabilisatoren, wie z.B. Phenole, insbesondere sterisch gehinderte Phenole, Verlaufs- und Rieselhilfsmittel, wie z.B. pyrogene Kieselsäuren sowie Füllstoffpartikel zugegeben werden. Vorzugsweise wird, bezogen auf das Gesamtgewicht an Komponenten im Pulver, soviel dieser Stoffe den Pulvern zugegeben, dass die für das erfindungsgemäße Pulver angegeben Konzentrationen für Füll- und/oder Hilfsstoffe eingehalten werden.To improve the processability or to further modify the powder, inorganic pigments, in particular colored pigments, such as e.g. Transition metal oxides, stabilizers, e.g. Phenols, in particular sterically hindered phenols, flow and flow aids, such. fumed silicas and filler particles are added. Preferably, based on the total weight of components in the powder, so much of these substances are added to the powders that the concentrations for fillers and / or auxiliaries stated for the powder according to the invention are maintained.
Gegenstand der vorliegenden Erfindung ist auch die Verwendung von erfindungsgemäßem Pulver zur Herstellung von Formkörpern in einem schichtweise arbeitenden und selektiv das Pulver verbindenden (Rapid-Prototyping- oder Rapid-Manufacturing-) Verfahren, bei denen erfindungsgemäße Pulver, die Polymer und ein Ammoniumpolyphosphat aufweisendes Flammschutzmittel, vorzugsweise jeweils in partikulärer Form aufweisen, eingesetzt werden.The present invention also provides the use of powder according to the invention for the production of moldings in a layer-wise and selectively powder-joining (rapid-prototyping or rapid-manufacturing) process, in which powders according to the invention, the polymer and a flame retardant comprising ammonium polyphosphate, preferably each in particulate form, are used.
Insbesondere ist Gegenstand der vorliegenden Erfindung die Verwendung des Pulvers zur Herstellung von Formkörpern durch selektives Lasersintern eines flammschutzmittelhaltigen Fällpulvers auf Basis eines Polyamid 12, welches eine Schmelztemperatur von 185 bis 189 °C, eine Schmelzenthalpie von 112 ± 17 J/g und eine Erstarrungstemperatur von 136 bis 145 °C aufweist und dessen Verwendung in
Die Laser-Sinter-Verfahren sind hinlänglich bekannt und beruhen auf dem selektiven Sintern von Polymerpartikeln, wobei Schichten von Polymerpartikeln kurz einem Laserlicht ausgesetzt werden und so die Polymerpartikel, die dem Laserlicht ausgesetzt waren, miteinander verbunden werden. Durch die aufeinanderfolgende Versinterung von Schichten von Polymerpartikeln werden dreidimensionale Objekte hergestellt. Einzelheiten zum Verfahren des selektiven Laser-Sinterns sind z.B. den Schriften
Wegen der Empfindlichkeit der Flammschutzmittel gegenüber Luft ist ein sorgfältiger Umgang bei der Handhabung der erfindungsgemäßen Pulver zu empfehlen. Insbesondere ist der längere Kontakt des erfindungsgemäßen Pulvers mit Luft bzw. Luftfeuchtigkeit zu vermeiden. Durch die Verwendung von hydrophober Rieselhilfe kann die Empfindlichkeit des erfindungsgemäßen Pulvers verringert werden, so dass eine Verringerung des E-Moduls, die gegebenenfalls durch die Zersetzungsprodukte von Ammoniumpolyphosphat bewirkt wird, vermieden werden kann.Because of the sensitivity of the flame retardant to air, careful handling of the powders according to the invention is recommended. In particular, the prolonged contact of the powder according to the invention with air or atmospheric moisture is to be avoided. Through the use of hydrophobic flow aid, the sensitivity of the powder according to the invention can be reduced, so that a reduction of the modulus of elasticity, which is optionally caused by the decomposition products of ammonium polyphosphate, can be avoided.
Die erfindungsgemäßen Formkörper, hergestellt durch ein Verfahren zum schichtweisen Aufbau von dreidimensionalen Gegenständen, bei dem selektiv Teile eines Pulvers, insbesondere des erfindungsgemäßen Pulvers, miteinander verbunden werden, wie z.B. dem selektiven Laser-Sintern, zeichnen sich dadurch aus, dass sie zumindest ein ammoniumpolyphosphathaltiges Flammschutzmittel und zumindest ein Polymer aufweisen oder aus zumindest einem ammoniumpolyphosphathaltiges Flammschutzmittel und zumindest einem Polymer bestehen. Vorzugsweise weisen die erfindungsgemäßen Formkörper zumindest ein Polyamid auf, welches pro Carbonamid-Gruppe mindestens 8 Kohlenstoffatome aufweist. Ganz besonders bevorzugt weisen erfindungsgemäße Formkörper zumindest ein Polyamid 612, Polyamid 11 und/oder ein Polyamid 12 oder Copolyamide, basierend auf diesen Polyamiden und zumindest ein Ammoniumpolyphosphat aufweisendes Flammschutzmittel auf.The shaped bodies according to the invention, produced by a process for the layered construction of three-dimensional objects, in which parts of a powder, in particular of the powder according to the invention, are interconnected selectively, such as selective laser sintering, are characterized in that they contain at least one ammonium polyphosphate flame retardant and at least one polymer or consist of at least one ammonium polyphosphate flame retardant and at least one polymer. The shaped bodies according to the invention preferably have at least one polyamide which has at least 8 carbon atoms per carbonamide group. Very particular preference is given to moldings according to the invention comprising at least one polyamide 612, polyamide 11 and / or a polyamide 12 or copolyamides based on these polyamides and at least one flame retardant comprising ammonium polyphosphate.
Das in dem erfindungsgemäßen Formkörper vorhandene Flammschutzmittel basiert auf Ammoniumpolyphosphat. Vorzugsweise weist der erfindungsgemäße Formkörper, bezogen auf die Summe der im Formkörper vorhandenen Komponenten, von 5 bis 50 Massen-% an ammoniumpolyphosphathaltigem Flammschutzmittel, bevorzugt von 10 bis 40 Massen-%, besonders bevorzugt von 20 bis 35 Massen-% und ganz besonders bevorzugt von 23 bis 34 Massen-% auf. Maximal beträgt der Anteil an ammoniumpolyphosphathaltigem Flammschutzmittel bevorzugt 50 Massen-% bezogen auf die Summe der im Formkörper vorhandenen Komponenten. Der Formkörper weist, bezogen auf die Summe der vorhandenen Polymere 30 - 35 Gew.-% Ammoniumpolyphosphat aufweisende Flammschutzmittel auf.The flame retardant present in the molding according to the invention is based on ammonium polyphosphate. Preferably, the shaped body according to the invention, based on the sum of the components present in the molding, of from 5 to 50% by mass of ammoniumpolyphosphathaltigem flame retardant, preferably from 10 to 40% by mass, more preferably from 20 to 35 mass% and most preferably from 23 to 34% by mass. The maximum amount of ammonium polyphosphate flame retardant is preferably 50% by mass, based on the sum of the components present in the molding. The molding has, based on the sum of the existing polymers on 30- 35 wt .-% ammonium polyphosphate having flame retardants.
Die Formkörper können neben Polymer und Flammschutzmittel außerdem Füllstoffe und/oder Hilfsstoffe und/oder Pigmente, wie z.B. thermische Stabilisatoren und/oder Oxidationsstabilisatoren wie z.B. sterisch gehinderte Phenolderivate aufweisen. Füllstoffe können z.B. Glas-, Keramikpartikel und auch Metallpartikel wie zum Beispiel Eisenkugeln, bzw. entsprechende Hohlkugeln sein. Bevorzugt weisen die erfindungsgemäßen Formkörper Glaspartikel, ganz besonders bevorzugt Glaskugeln auf. Vorzugsweise weisen erfindungsgemäße Formkörper weniger als 3 Gew.-%, vorzugsweise von 0,001 bis 2 Massen-% und ganz besonders bevorzugt von 0,05 bis 1 Massen-% solcher Hilfsstoffe bezogen auf die Summe der vorhandenen Komponenten auf. Ebenso bevorzugt weisen erfindungsgemäße Formkörper weniger als 75 Massen-%, bevorzugt von 0,001 bis 70 Massen-%, besonders bevorzugt von 0,05 bis 50 Massen-% und ganz besonders bevorzugt von 0,5 bis 25 Massen-% solcher Füllstoffe bezogen auf die Summe der vorhandenen Komponenten auf.In addition to polymers and flameproofing agents, the shaped articles may also contain fillers and / or auxiliaries and / or pigments, such as e.g. thermal stabilizers and / or oxidation stabilizers, e.g. have sterically hindered phenol derivatives. Fillers may e.g. Glass, ceramic particles and metal particles such as iron balls, or corresponding hollow balls be. The shaped bodies according to the invention preferably have glass particles, very particularly preferably glass spheres. Preferably, moldings according to the invention have less than 3% by weight, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass, of such auxiliaries, based on the sum of the components present. Likewise, moldings according to the invention preferably comprise less than 75% by mass, preferably from 0.001 to 70% by mass, more preferably from 0.05 to 50% by mass, and very particularly preferably from 0.5 to 25% by mass of such fillers, based on Sum of existing components.
Die folgenden Beispiele sollen die erfindungsgemäße pulverförmige Komposition sowie deren Verwendung beschreiben, ohne die Erfindung auf die Beispiele einzuschränken.The following examples are intended to describe the powdery composition according to the invention and its use, without restricting the invention to the examples.
Die in den nachfolgenden Beispielen durchgeführte Bestimmung der BET-Oberfläche erfolgte nach DIN 66 131. Die Schüttdichte wurde mit einer Apparatur gemäß DIN 53 466 ermittelt. Die Messwerte der Laserbeugung wurden an einem Malvem Mastersizer S, Ver. 2.18 erhalten.The determination of the BET surface area carried out in the following examples was carried out according to DIN 66 131. The bulk density was determined using an apparatus according to DIN 53 466. The laser diffraction measurements were taken on a Malvem Mastersizer S, Ver. 2.18 received.
40 kg ungeregeltes, durch hydrolytische Polymerisation hergestelltes PA 12 hergestellt in Anlehnung an
40 kg geregeltes, durch hydrolytische Polymerisation hergestelltes PA 12, Typ Vestamid L1600 der Degussa AG, werden mit 0,3 kg IRGANOX ® 245 und 12 kg (30 Teile) Flammschutzmittel (Budit 3076 DCD, Budenheim Iberica) bei 220 °C in einer Zweiwellen-Compoundiermaschine (Bersttorf ZE25) extrudiert und als Strang granuliert. Das Granulat wird anschließend bei tiefen Temperaturen (-40 °C) in einer Prallmühle auf eine Korngrößenverteilung zwischen 0 und 120 µm vermahlen. Anschließend wurden 40 g Aerosil 200 (0,1 Teile) bei Raumtemperatur und 500 U/min 3 Minuten untergemischt.40 kg regulated, by hydrolytic polymerization produced PA 12, type Vestamid L1600 Degussa AG, with 0.3 kg IRGANOX ® 245 and 12 kg (30 parts) flame retardant (Budit 3076 DCD, Budenheim Iberica) at 220 ° C in a two-shaft -Compoundiermaschine (Bersttorf ZE25) extruded and granulated as a strand. The granules are then ground at low temperatures (-40 ° C) in an impact mill to a particle size distribution between 0 and 120 microns. Subsequently, 40 g of Aerosil 200 (0.1 part) were mixed in at room temperature and 500 rpm for 3 minutes.
Zu 1900 g (65 Teile) Polyamid 12-Pulver, hergestellt gemäß
Unter den selben Bedingungen wurden weitere Pulver hergestellt, die 10, 20, 25, 30 und 35 Teile des Flammschutzmittels Budit 3076 DCD-2000 aufweisen.Under the same conditions, further powders were made comprising 10, 20, 25, 30 and 35 parts of the flame retardant Budit 3076 DCD-2000.
Zu 1900 g (70 Teile) Polyamid 12-Pulver, hergestellt gemäß
Zu 1900 g (80 Teile) Polyamid 12-Pulver, hergestellt gemäß
Unter den selben Bedingungen wurden weitere Pulver hergestellt, die 10, 25, 30 und 35 Teile des Flammschutzmittels Exolit AP 422 aufweisen.Under the same conditions, further powders were produced which have 10, 25, 30 and 35 parts of the flame retardant Exolit AP 422.
Die Pulver aus den Beispielen 1 bis 4 wurden auf einer Laser-Sinter-Maschine zu Stäben für den Brandschutztest gemäß UL94V sowie zu Mehrzweckstäben nach ISO 3167 verbaut. An letzteren Bauteilen wurden mechanische Werte mittels Zugversuch nach EN ISO 527 ermittelt (Tabelle 1). Die UL-Stäbe wurden für den vertikalen Brenntest nach UL94V (Underwriters Laboratories Inc.) verwendet. Die Stäbe haben die Sollabmessungen 3,2*10*80 mm. Die Herstellung erfolgte jeweils auf einer Laser-Sinter-Maschine EOSINT P360 der Firma EOS GmbH.
Es ist deutlich zu erkennen, dass durch die Zugabe von auf Ammoniumpolyphosphat basierendem Flammschutzmittel zum Polymerpulver Formkörper hergestellt werden können, die eine deutlich bessere Einstufung nach UL aufweisen. Durch die Zugabe des Flammschutzmittels wird außerdem eine Erhöhung des Elastizitätsmoduls und der Zugfestigkeit erzielt, wobei allerdings gleichzeitig die Reißdehnung verringert wird.It can be clearly seen that the addition of ammonium polyphosphate-based flame retardant to the polymer powder makes it possible to produce moldings which have a significantly better UL classification. By adding the flame retardant In addition, an increase in the modulus of elasticity and the tensile strength is achieved, but at the same time the elongation at break is reduced.
Claims (36)
- Pulverulent composition for processing in a process for the layer-by-layer build-up of three-dimensional objects by selectively bonding portions of the powder to one another,
characterized in that
the powder comprises at least one polymer and at least one flame retardant comprising ammonium polyphosphate and has a maximum particle size of ≤ 150 µm. - Powder according to Claim 1,
characterized in that
the polymer was prepared by milling, precipitation, and/or anionic polymerization, or by a combination of these, or by subsequent fractionation. - Powder according to Claim 1 or 2,
characterized in that
the polymer is a homo- or copolymer selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, poly-(N-methylmethacrylimides) (PMMI), polymethyl methacrylate (PMMA), ionomer, polyamide, copolyester, copolyamides, terpolymers, acrylonitrile-butadiene-styrene copolymers (ABS), or is a mixture of these. - Powder according to at least one of Claims 1 to 3,
characterized in that
the powder comprises a nylon-6,12, nylon-11, or nylon-12, or copolyamides based on the aforementioned polyamides. - Powder according to at least one of Claims 1 to 4,
characterized in that
the polymer has a melting point of from 50 to 350°C. - Powder according to Claim 5,
characterized in that
the polymer has a melting point of from 70 to 200°C. - Powder according to at least one of Claims 1 to 6,
characterized in that
the powder has a median particle size of from 20 to 100 µm. - Powder according to at least one of Claims 1 to 7,
characterized in that
it also comprises at least one auxiliary and/or at least one filler, and/or at least one pigment. - Powder according to Claim 8,
characterized in that
it comprises flow aid as auxiliary. - Powder according to any of Claims 1 to 9,
characterized in that
the ammonium polyphosphate contains from 10 to 35% by weight of phosphorus. - Powder according to any of Claims 1 to 10,
characterized in that
the flame retardant component comprises synergists alongside the ammonium polyphosphate. - Powder according to any of Claims 1 to 11,
characterized in that
the powder comprises the flame retardant component in pulverulent form with a median particle size of from 1 to 50 µm. - Powder according to any of Claims 1 to 12,
characterized in that
the flame retardant component is in pulverulent and coated form. - Sinter powder according to any of Claims 1 to 13,
characterized in that
the powder comprises, based on the entirety of polyamides present in the powder, from 0.01 to 30% by weight of metal soap. - Sinter powder according to Claim 14,
characterized in that
the powder comprises, based on the entirety of polyamides present in the powder, from 0.5 to 15% by weight of metal soap. - Sinter powder according to any of Claims 1 to 14,
characterized in that
the powder comprises fine metal soap particles mixed with polyamide particles. - Sinter powder according to any of Claims 1 to 14,
characterized in that
the powder comprises metal soaps incorporated within polyamide particles. - Sinter powder according to at least one of Claims 1 to 17,
characterized in that
the metal soaps are the alkali metal or alkaline earth metal salts of the underlying alkanemonocarboxylic acids or dimer acids. - Sinter powder according to at least one of Claims 1 to 18,
characterized in that
the metal soaps are the sodium or calcium salts of the underlying alkanimonocarboxylic acids or dimers acids. - Process for preparing powder according to at least one of Claims 1 to 19,
characterized in that
at least one polymer with a flame retardant comprising ammonium polyphosphate is mixed. - Process according to Claim 14,
characterized in that
polymer powder obtained by reprecipitation or milling is mixed in a dry blend process with the flame retardant comprising ammonium polyphosphate. - Process according to Claim 14,
characterized in that
the flame retardant comprising ammonium polyphosphate is compounded into a melt of polymer, and the resultant mixture is processed by milling to give powder. - Use of powders according to at least one of Claims 1 to 13 for producing moldings by a layer-by-layer process which selectively bonds the powder.
- Use according to Claim 17,
characterized in that
moldings are produced by selective laser sintering, selective inhibition of the bonding of powders, 3D printing, or a microwave process. - Molding, produced by a process for the layer-by-layer build-up of three-dimensional objects by selectively bonding portions of a powder to one another,
characterized in that
it comprises at least one flame retardant comprising ammonium polyphosphate and comprises at least one polymer. - Molding according to Claim 19,
characterized in that
it comprises a polyamide which contains at least 8 carbon atoms per carboxamide group. - Molding according to Claim 19 or 20,
characterized in that
it comprises nylon-6,12, nylon-11 and/or nylon-12, or copolyamides based on these polyamides. - Molding according to any of Claims 19 to 21,
characterized in that
based on the entirety of the components present, it comprises from 5 to 50% by weight of flame retardant comprising ammonium polyphosphate. - Molding according to Claim 22,
characterized in that,
based on the entirety of the polymers present, it comprises from 30 to 35% by weight of flame retardant comprising ammonium polyphosphate. - Molding according to at least one of Claims 19 to 23,
characterized in that
it comprises fillers and/or pigments. - Molding according to any of the preceding claims,
characterized in that,
based on the entirety of the polyamides present in the powder, it comprises from 0.01 to 30% by weight of metal soap. - Molding according to any of the preceding claims,
characterized in that,
based on the entirety of the polyamides present in the powder, it comprises from 0.5 to 15% by weight of metal soap. - Molding according to any of the preceding claims,
characterized in that
it comprises fine metal soap particles mixed with polyamide particles. - Molding according to any of the preceding claims,
characterized in that
the powder comprises metal soaps incorporated within polyamide particles. - Molding according to any of the preceding claims,
characterized in that
the metal soaps are the alkali metal or alkaline earth metal salts of the underlying alkanemonocarboxylic acids or dimer acids. - Molding according to any of the preceding claims,
characterized in that
the metal soaps are the sodium or calcium salts of the underlying alkanemonocarboxylic acids or dimer acids.
Priority Applications (1)
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PL04766029T PL1648958T3 (en) | 2003-07-25 | 2004-06-03 | Powdery composition of a polymer and a flameproofing agent containing ammonium polyphosphate, method for the production thereof, and moulded body produced from said powder |
Applications Claiming Priority (3)
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DE10333936 | 2003-07-25 | ||
DE102004001324A DE102004001324A1 (en) | 2003-07-25 | 2004-01-08 | Powder composition used in the layerwise buildup of three-dimensional articles comprises a polymer and an ammonium polyphosphate flame retardant |
PCT/EP2004/051009 WO2005010087A1 (en) | 2003-07-25 | 2004-06-03 | Powdery composition of a polymer and a flameproofing agent containing ammonium polyphosphate, method for the production thereof, and moulded body produced from said powder |
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EP1648958B1 true EP1648958B1 (en) | 2007-08-01 |
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US (3) | US20060223928A1 (en) |
EP (1) | EP1648958B1 (en) |
JP (1) | JP4589321B2 (en) |
KR (1) | KR20060066712A (en) |
CN (1) | CN1856534B (en) |
AT (1) | ATE368705T1 (en) |
AU (1) | AU2004259091A1 (en) |
CA (1) | CA2533419A1 (en) |
DE (2) | DE102004001324A1 (en) |
ES (1) | ES2290753T3 (en) |
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-
2004
- 2004-01-08 DE DE102004001324A patent/DE102004001324A1/en not_active Withdrawn
- 2004-06-03 DE DE502004004522T patent/DE502004004522D1/en not_active Expired - Lifetime
- 2004-06-03 AU AU2004259091A patent/AU2004259091A1/en not_active Abandoned
- 2004-06-03 WO PCT/EP2004/051009 patent/WO2005010087A1/en active IP Right Grant
- 2004-06-03 KR KR1020067001716A patent/KR20060066712A/en not_active Application Discontinuation
- 2004-06-03 EP EP04766029A patent/EP1648958B1/en not_active Expired - Lifetime
- 2004-06-03 CA CA002533419A patent/CA2533419A1/en not_active Abandoned
- 2004-06-03 ES ES04766029T patent/ES2290753T3/en not_active Expired - Lifetime
- 2004-06-03 CN CN2004800278399A patent/CN1856534B/en not_active Expired - Lifetime
- 2004-06-03 JP JP2006521562A patent/JP4589321B2/en not_active Expired - Fee Related
- 2004-06-03 US US10/565,779 patent/US20060223928A1/en not_active Abandoned
- 2004-06-03 AT AT04766029T patent/ATE368705T1/en not_active IP Right Cessation
- 2004-06-03 PL PL04766029T patent/PL1648958T3/en unknown
- 2004-07-19 TW TW093121515A patent/TW200505978A/en unknown
-
2006
- 2006-02-22 NO NO20060872A patent/NO20060872L/en not_active Application Discontinuation
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2008
- 2008-12-11 US US12/332,607 patent/US7795339B2/en not_active Expired - Lifetime
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JP2006528717A (en) | 2006-12-21 |
US20090088508A1 (en) | 2009-04-02 |
US20060223928A1 (en) | 2006-10-05 |
JP4589321B2 (en) | 2010-12-01 |
KR20060066712A (en) | 2006-06-16 |
PL1648958T3 (en) | 2007-12-31 |
DE502004004522D1 (en) | 2007-09-13 |
ATE368705T1 (en) | 2007-08-15 |
AU2004259091A1 (en) | 2005-02-03 |
US20100324190A1 (en) | 2010-12-23 |
WO2005010087A1 (en) | 2005-02-03 |
EP1648958A1 (en) | 2006-04-26 |
NO20060872L (en) | 2006-02-22 |
CN1856534A (en) | 2006-11-01 |
CA2533419A1 (en) | 2005-02-03 |
TW200505978A (en) | 2005-02-16 |
DE102004001324A1 (en) | 2005-02-10 |
CN1856534B (en) | 2012-11-14 |
US8119715B2 (en) | 2012-02-21 |
ES2290753T3 (en) | 2008-02-16 |
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